Paint remover composition



Patented May 16, 1950 I PierEine-'rv eenen:

` atomes PAINT.REMo.vER COMPOSITION Lester LEE `Kil'entze'1,-'`WyandottefMiche;znssignoirztolf Wyandotte Cliemi'alsf Corporation, Wyandotte, Mich;,-acorporatr'of Michigan n v Y Nor Drawing. VApplication Novelli-bn-1194 5}f` serial'Nb. 626,172 v co-solvent, in addition toits paintsolfviit'proper-A ties; functions'as" a blendingagent' for the, meth-V Y deslablein'a paintrem'ove'r'f'since tlieyfrco'ntributelf both' to thev reduction' 'off' tiixreT and? labor required for* stripping; as Well fiasftof"V the-"convenience 'f andi" eflicien'cy of application*ofA remove to sur-facesTv ducing" 'a' thixoti'blpic,cornposition. The jloresent'` .1, application isacordingly a; continuation-impart" il of myfaforesaidcoepending application Serial No. 'Y

ert'iesi-'f non-inammabilityfloyv rate of evapo,"

ratio'nrandfemovability or rinsibility Yby water *n entre?if-*ajsmallamb'untfi -v A greatly-"inprovesithev-stri' chlorinated? solvents; and@ that@ trici 'presen fraai" that* 'some organic and"` miniem; :isaiasiV depressi rath'erthan.' accelerate; th'elpaint:strip;.fA ping action if the chlorinated hydrocarbon solvents, demonstratesthe unusual and unpredictable nature of the discovery upon which "my in* vention is foundedlv yI have alsodiscovered'ithat wher'ef methylene chloride is used as the lcliloilnated' aliphatic hydrocarbonlsolvent, with the presence-of relatively smallamountof Water and the addition of methyl cellulose and a blending' agent which is a co-solvent fori-the methylene; 'chloride and for the methyl cellulose, thenthe desired-thixotropic property is imparted to the paintl\ remover or stripping composition. In my copending application Serial No'. 50911211 filed Novein'ber 5, 1943, now U. S. Pat. No; 2',433',5'17,1issued` D'ec. 30, 1947, I have disclosed'a paitieihove'r'formulation Coni After'removing the paint Aorthe' like from the sur.- Y face', my"cornpositions""a1so" leave such surface"y Whether it hanf-fetale?, Wood, in suchondtin" that may be' m'm relat d ends, Y'tli followindscrption sets ifor'thg.

'Paint-l'lstriiltiling;powerV ofthe above-mentioned 1 1 Vent's@ v Formic Plcric K. AceticA 1ilyo1: y1phcsphmgm,`

salicylic Butyric` Y Carbolicz` r addition tol tlobjctivesand advantages above" noted, the" paint. removerf compositions ',of i myinyen'tion" possess tliejhighly bene'cial prop-` A tely reiifnis`hecl;` since they Y iv" actionV on most." metalsl Y the blending agent in the compositions embodying the principle of my invention:

Methyl alcohol Ethyl alcohol Butyl alcohol Ethylene chlorhydrin Isopropyl alcohol 2 methyl 2, 4 pentanediol Hexanol Amyl alcohol Ethylene glycol Di-ethylenefglycol ,mono-ethyl ether, or Ethyl Carbitol Dibutoxyethane Ethylene glycol monobutyl ether, or "Butyl Cellosolve" Propylene glycol Ethylene glycol mono-ethyl ether; jor Ethyl ,Cel-

losolve il but it is fairly soluble in water and acids. Whether the methyl cellulose fibers become truly dissolved or hydrated and dispersed is not de-l nitely known. In the case of methylene chloride, the presence of an ingredient which is a cosolvent for the methylene chloride and the methyl cellulose containing water, such as an amine as disclosed in my aforesaid co-pending application Serial No. 509,121, or a blending agent selected from those hereinabove listed, isI all important and critical in imparting the thixotropic propertiesto the composition.`

Additional ingredients including gan evaporation retardant, such as paraffin wax; and wetting agents, such as alkylated aromatic sodium sul-j fonates may also be incorporated to advantage into the-composition. These wetting agents are of particular advantage because they impart easier removability of the paint remover composition by water, even when water-insoluble materials, such as parain wax, are present.

' "Wetting agents of the alkyl aryl sulfonate type presntfthus contributing to-.the achievement of. the desiredthixotropic propertyf the composition as av whole.

solvents in generak have .the vtendency to decomposeafter a period of ,time orto-hydrolyze in.,

thehpresenceof moisture, light, and .elevated temperatureatoformhydrochlorc acid. How,- ever, such a possible latent or inherent presence of acid in thechlorinated` hydrocarbon solvent is .obviously not included within theV purviewV ofv myinvent'on, since not -only does my invention contemplate the additionpf any .acid not inherently, present orgenerated inthe Vchlorinated hydrocarbon,v lbut also, hydrochloric acid. is one of those acids which have been found to depress rather than promote, the stripping. power of thev solvent. l,

The.' amount of water incorporated into the mixture vselected from theabovesolvents, acids and blending agentsVhas ,been found-to be crit ical.v .The amount of water shouldbe no greater thanthatwhch is capable of going into solution `with the remaining ingredients of the mixturei. e., whereby the mixture willfremain in a.

single phase. If vmore than this maximum amount of water is added, not only. will an emulsionbe `formed, which, on standing tends to separateput into layers (i. e.. two phases), but Valso theA stripping power of the-composition willbeV decreased. In my preferred formulations, cornof water present is found to be in the range of 0.071% vto.t.0% -by weightof the total composition.

Below this range of watercontent, the enhanced4 stripping, power is notA obtained .and above vthis range the thixotropic property is no longer maintained, nor is a single phase mixture achieved,

and maintained.

Methyl' cellulose within the commercially deso pears to be unique ,in imparting thixotropic propy ignated viscosity range of V15 to 4000 c. p. s.ap,

erties to the composition. Methyl cellulose havj ing a methoxy content of about 32% is preferred.

Methyl cellulose is insoluble land immiscible with the.; chlorinated aliphatic hydrocarbon: solvent; '(5

have been found to be quite satisfactory in the formulation. of compositions embodying the principle of my invention. Specifically, alkyl arylsulfonate wetting agents are available on the market `under the trade names of "Santomerse Santomerse proportion-of terpenes and about 20% water,-

content.4 ',The alkyl and .aryl groups of such latter formA of alkyl aryl sulfonate are-not denitely knownv or publicized, such informationfbeing ,the y private property of the manufacturer:r `of such 1.,

product. -Wetsit Concentratedis particularly suitable since it contains approximately 20%- water and thus serves as a convenient means for adding the water ingredient to the composition, making it unnecessary to add water separately as there is enough water in such wetting agent to ysatisfy the formulationy requirements.

Generally outlined, theA paint remover com-l positionsof my invention are combined or formulated by mixing together the chlorinated sol-.. vent, the methyl cellulose, the acid, the water, and the blending agent, in the order named and at room temperature. Melted parafn wax, ifpresent, is incorporated directly after the solvent.r The extraordinary improvement in the stripping 'power of 'the chlorinated vsolvent byv the.. addition of small amounts Vofwater is shown in4 the following Table I, wheremixtures of methylene chloride -andvarving amounts of water were Y applied yto painted test -panels uNos. 14105 and f 14109 made according to -specications as hereinafter referred to, andthe time required to strip the paint coating from such panels duly notedz ,l Saturated solution ofwaterin methylene chloride.A

lllfey methylene chloride usedllinethe-emlxtures of fthe foregoing -i-TablevJI Was-elrst-:.caretullyMdistilled to remove any possible trace of waters'r The pronounced activating effect of certain selected acids on the strippingpgwer of the chlocelerate the strippinglpowergof the chlorinated solvent,A isiurther shown ,in .the ,following .Tablev Illuiwhere` mixtureswof methylene chloride, with water and salicylic. acid-(added .separatelynand jointly)v wereapplied to I T. S; Navy.Meronauti0211.35.;y

Sneciiatign test :panels 72 amil` '15E ,as recited in Navy Aeronautical lSpecification C-113, Amendment-2; and United States Army Air Force test.,panels Nos.A 14105v and A14109, Aasvrecited, in ArmY-.Ar F1orce. Specication No.14119`..` The de.- tailed description. vof .these,strpping-tstpanelslis set Iortlr in my io-pending. applicationSerialfNQ- 509,121and need not be' helerepeated.5`

Table Thedollowing yexamples "of .formulations-ofiinf gredielits 4furtlfierqserveto illustratelmy-invention; ,such `examples :being/givenf-by 'way offillustrationg-l rinated solvent 1s lllustratedNin the following :latf;lier''thanxllmitatiomf Table ,Il where `varying. 010911111151111100%glacial acetiqacid were 4,added to methylene chloride, and l f suchpmixtures:similarly, tested as in the case of @mamme-f1? Table' i12 K 10 lrrmulanlon N0.;10051j Table I!" ,y

w.. 'Percentf Percent y. r Amount: yv Waters Stripping lPoyyer (time.in l l j Weight;l Content,..-

m-amplrss l 'ff ,005811 C08 Wgcof panelsl" 'g" 5'lP/lethg1lneohlorlde 100ml--- v 8.18 Amd Methyl Cellulose 4000 0. p. s), 1g g 0.95 1410s Y 14100 A0000 Acid (Glacial)` :ml- 0.03 Formic Acid (90% 1 ml---" Y 0. 77 Wetsit Concentrated A51111;...` f 3.20 0.000 over 10,000 9,000 Methanol ..19 ml 10 0.2., 500. 180.5 20A.. K Y l.0v `00\ 100.00 .717

10.00l 10v 28.0- k 31.5 0 40 The Vforegoing :constituents-were-comblned-=iby 02.5 00 4 03.3 00 2 5 `Am1x1ng `together inthe above. gillenprderfatroo i igg temperaturef-, with the eizceptionoLthe-lparalng, A wax-which-was-f1rst melted. `The resulting com- Y position is'famber, in color and clear at tempera- The Aremarkallle ability of relatively.T small ture"above"'Fg'becomng^-slightly-milky-'toamo.unts.o...water and vacidito enhance or acaofopaque at lower temperatures as the wax precipitates. The composition is thixotropic and mayl be ,applied rby;dialling-.,1-.brushinsr ,swabbine Oraspaying-f Dnmedatelyi gupsmV @application to..

the surface from which the paint, varnish, silenzie151,`

--furrliture,k machine-.parts 'aircraft-watercraft..

and :brief-like. The.,following-exemplary ,formulation is `one. which thesacidblendinglagent :and .wettineasent 1 Merlin..

Stripping Power (tlme-'inseconds to completely 'l Coating softened, but notloosened.

Itghas been found that the -stripping,jpower ot,... metlgy r,ne chloride-is especially enhancedlbyfthef. additi. ...111.01 .waterfandfa-- monQarboXylic acid of 1 to 3 carbon atoms, via;foxlnihaceticanlpige?.v pigni. acids. Thus, .9, compositionof vvmethylene chloride y..10 parts, formic. acid 0.1 part and .water 0.1v part l(allparts :by ,yolume) CQmpletelyloosened the coating on a #14105 test panel. in, ylilsecoxlds :v and on a #14109 test panel in 50 seconds.

A composition containing methylene chloride 10;;pa11ts, acetic'acid 0.1 part and water 0.1 part (allparts I by volume) completely -l'oosenedthe A coating on a 4ib14105-testl panel `in-2 0 seconds 4and f orti-@$14 109 test -panel i'n- 1 10 seconds;

A, composition of methylene -chloride -10 A"parts-,- prgpionic acid 0:1 part l'andWater-i 0;1 y"part/f (all parts by volume) -completelywloesencMalle-coatings'uitz l Methyl-Cellulose.; u

Methylene Chloride Para-ffm 7 The foregoiiigconstituents were combined inv the same manner as in Example 1. The resulting composition is similar in physical characteristics and properties as that of the composition of Example 1 with the exception thatthe parafn wax remains in solution at a temperature of 74 F. and above.

By omitting the methyl cellulose and blending agent, the thixotropic property is correspondingly removed, but the stripping power remains equallyhigh. The following exemplary formulationhas the methyl cellulose and blending agent omitted'. It is well suited for use as an immersionor tank type of paint remover.

Example 3 [Formulation No. 1666] The foregoing composition isa non-thixotropic, light amber, Water-thin liquid for use in tank stripping. Y Y

If desired, a Smallamount of distinctive coloring agent, such'as Patent Blue dye may be added to any one of the compositions of the foregoing examples. j

As previously herein indicated, an amine such as disclosed in my aforesaid pending application Serial No. 509,121, also functions as a blending agent or co-solvent for the methylene chloride, methyl cellulose and water. The following formulation, wherein cyclohexylamine is employed in place of one of the alcohol or ether blending agents herein specified, thus also produces a thixotropic composition.

.,.Patent Blue dye is also known as Xylenblau; for

' ,its chemical constituency, refer to Farben-Chemie Fierz- David and Blangey (J. N. Edwards, 1944), p. 286,

The foregoing composition is likewise thixo- Another formulation in which phenol or car4 bolic acid is employed as the acid ingredient, is as follows:

Example 5- {Formulation No. 2346 Per Cent Amount by Weight f. hanced.

Methylene Chloride Paratlin Wax Methyl Cellulose (1,5 c. p. s.) Wetsit Concentated" Water Glass Phenol (s0lid)..

"f The remarkable stripping ability of the composition of my invention as exemplied by the foregoing examples, is illustrated by the following test results:

. Stripping Power (time in seconds required to loosen coating comv pletely from the following num- Composition bered test panels) `72 70E 75E 14105 14109- i Example l l0 l5 l0 40 40 Example 2.- l0 l0 l0 50 50 Example 3-. l0 15 10 40 40 l Example 5. 60 45 30 20 150 The amount of water present in the paint re- `mover formulations embodying the principle'of my invention, particularly where methyl cellulose is present, is preferably not over 6.0% 'by weight of the total composition. Above this limit a single phase mixture cannot be obtained, and moreover, the strippingpower is not further en- The.. acid constituent is. preferably maintained in thevrange of 0.1 to 50% by weight of the total composition, since this range also is the one in which the optimum benefit to the" stripping power on the majority of paints, var- 4"nishes, lacquers and enamels is obtained. Them chlorinated solvent range is from to 95%.;

The paint remover compositions of my invention being water rinsible, may be easily and elllciently removed after stripping function is com- "plete'd'f'simply'by flushing or scrubbing 'oi with' water.

tropic as in the case of the compositions, of Ex- 'i amples 1 and 2.above and is blue in color.' y The cyclohexylamine constituent, being a co-solvent for the methylene chloride and the methyl cellulose, acts as a blending agent.

Equivalent modes of practicing my invention may be followed provided that they are within the scope and purview of the appended claim.

I, therefore, distinctly claim and particularly point vout as my invention:

A paint remover having'thixotropic properties and consisting of the following ingredients pres- 'ent in approximately the respectively listed pro-A portions' by weight:y

Per cent by weightl 9 and the balance dodecylbenzene sodium sulfonate, the latter sulfonate containing sufficient Water which together With the Water content of said formic acid ingredient, is equal to 0.717% of the total composition.

LESTER E. KUENTZEL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,095,270 Ellis May 5, 1914 1,147,849 Ellis July 27, 1915 1,147,850 Ellis July 27, 1915 OTHER REFERENCES Bennett: Chemical Formulary, vol. 1 (1933), page 385.

Synthetic Organic Chemicals, Carbide and Carbon Chemical Corporation, N. Y., 10th ed. (1940), page 52. 

